Catalyst



flfatenteol Aug. 7, 1945 r oFFic CATALYST ration of Maine 1 John W. Tater, Chicago, a, assigno'r to vsiiicimi- Refining Company, New York.- N. Y., a corpo- No Drawinz. Application lilayzii, 1943,

' Serial No. 489,0W

4 Gianna.- rom 64) v This invention relates to the catalytic The production of aminesand nitrilesby the catalytic amination of olefinlc hydrocarbons has been found to be an especially promising and valuable source of such materials for use in the synthesis of various compounds including, the production of synthetic rubber and other nitrogencontaining materials. Various catalysts have.

been used successfully in such amination operations. Hovpev er, cobalt has been found to be especially effective. Generally, the animation is effected by br n ng an ature of hydrocarbon and ammonia into contact with the catalyst at an I elevated temperature and pressure.

Heretofore, in the catalytic animation of oleilnic hydrocarbons'with ammonia, the desired amination reaction has invariably been accom- 'panied by a plurality of competing side reactions,

W 1atlon of olefinlc hydrocarbons-and more particuv larly to improvements in such amlnationoperations especially with respect to the catalyst em- 'terfered with by any substantial disintegration I of the catalyst pellets. Accordingly, it is highly desirable that such disintegration be avoided so far: as possible. v My research experience in this field vindicates that the tendency of the catalyst to disintegrate is closely associated with'the extent of carbon deposition on the catalyst. This carbon deposit results from the competitive cracking reaction which not only tends to decrease the yieldof the desired product but fouls the catalyst and,-lf permitted to proceed to too greatan extent, results m a bmdingtoeether of the-catalyst bed so as to interfere with theuniformity'of flow of the reactants and reactivating gases therethrough and makes difilcult the removal of the catalyst 'from the reactor.-

including polymerization, and cracking of the hydrocarbon, which tend to reduce materially the -.yield of the desired nitrogen-containing compound. Catalysts comprising cobalt suspended on a suitable carrier have been found to be perticularlyeffective in selectively catalyzing the de-'-.

. sired amination reaction and relatively repressmg. the undesirable competing side reactions.

. After a period of operation the catalyst has been found to lose its selectivity to aqgreater' or less extent and is reactivated by treatment with hydrogen at anelevated temperature. After continued use with intermittent reactivation, the

catalyst becomes contaminated with carbon to such an extent that regeneration by burning 0d the carbon and subsequently reducing the catalyst, as by treating with hydrogen, becomes nec essary.

An advantageous method ef carrylng out the amination operation involves the use of the catalyst in the form of pellets and passing the olefin-ammonia mixture through abed of the pol leted catalyst. f Periodically the passage of the admixture through the catalyst is discontinued, the reaction chamber drained and purged and the catalyst reactivated or regenerated in situ or the catalyst may be removed from the reaction ch c-m her to another vessel for reactivation or regeneratiorfand subsequently returned to the reactor for further use;

In such operations the uniform flow of the olefin-ammonia mixtureend of the reactivating hydrogen tln' the catalyst is materially in- My present invention provides improvements in h the ation of olefluic hydrocarbons whereby many of the difliculties heretofore experienced are avoided or materially reduced. Briefly, my

invention provides an improved processwhereby olefinic hydrocarbons are reacted with ammonia in the presence of a catalyst comprising cobalt suspended on a suitable carrier and promoted by the presence of manganous oxide.

In accordance with my improved process, the objectionable side reactions are-materially repressed and the uniformity of operation and the useful lifeof the catalyst substantially improved.

' For example the rate of polymerization of the claims is materially reduced. Further, the rate at which products of cracking reactions are formed and the rate at which carbon is deposited on the catalyst are substantially reduced. Also, therate of disintegration of the catalyst is materially reduced, the uniformity of the operation, promoted and the useful life of the catalyst pro-. longed.

, T In addition to the foregoing,- the amination stance actonitrile, normal butyronitrlle, lsobutyronitrile and substantial proportions of unldentified nitrogen compounds,' are produced.

These nitrlles would normally be satisfactorily separated by fractional distillation. However, the nitrlle fractions are usually contaminated by so "polymerization products boiling within the reuse readily separated therefrom.

2 4 of the respective nitriles and accordingly In accordance with my improved process, the

productionbf suchcontaminants is materially reduced and, consequently, substantially pure nitrile products may be obtained by fractionation without resort to complicated separation procedure. In the preparation ofa catalyst" used in accordance' with my present invention, various known are not lystsuspension is then reduced by passing hydrocarriers may be used. For example, I have used consisting essentially of the silicaremains of diatoms of the type-which has been classified asmarine plankton diatoms and containing a" minor proportion of A1203, more fully described in my co-pending 'application'Serial No. 444,095,

-with' particular advantage diatomaceous silica gen in contact with the mass at a temperature 01 '650-750 F. for a period of about 12 hours or more and is ready for use. I

Thecatalyst thus produced will be found tc contain about 50% of the cobalt catalyst and about 1% of the manganous oxide promoter suspended on the carrier.- These proportions may be variedover av considerable range but I have filed May 22,1942, such as currently sold under the tradename Snow Floss. One mayalso use a hydrated magnesium silicate, preferably a synthetic magnesium silicate of high purity such as is more fully described in my co-pending a'ppli- .cationserial No. 444,096, filed May 22, 1942, and

heat-treatment, as more which is currently marketed under the tradename Magnesol or an acid-treated bentonite clay which has been subjected to a subsequent fully described in my co-pending application Serial No. 444,097, filed May 22, 1942, and which is currently marketed under the tradename Super-Filtrol. However, I have found the diatomaceous silica such as sold under the tradename Snow Floss to be espe-..

purpose of my present invencially suited for the tion.

Aparticularly advantageous catalyst for use 0 in. accordance with my present invention, comprising my manganous oxide .promoter, may be 1 prepared as follows: There is dissolved in 10 -g'allons'of distilled water, 6360 grams, approximately 25.5 moles, of cobalt acetate tetrahydrate.

The solution is then filtered and there is added the mixture stirred vigorously for about one hour. 3300 grams, approximately 31.2 moles, of anhydrous CP sodium carbonate is dissolved in l gallons'of distilled water, resultant solution added to the'cobalt solution as a precipitant. This addition is carried out at such a rate that about half of the carbonate solution is added I is then continued for about half an The stirring hour and the remaining carbonate solution added in a similar manner; The resulting slurry is then stirred forabout an hour and allowed to stand over night Thereafter, the

over axperiod of about one hour.

solid material iswashed by found about50% cobalt and about 1% mang'anous oxide, to be generally satisfactory.

The advantagesderived from the use of the manganous oxide promoter, in accordance with my present inventiomwill be specifically illustrated by reference to four catalytic amination operations carried out under comparable conditions. In each of these operations the catalyst employed comprised cobalt suspended on "Snow Floss," prepared substantially as previously described except that in the preparation of the catalysts used in two of the operations the man- C and D. Each catalyst ganous oxide promoter was omitted. The respective catalyst and the operations in which they were employed will be identified herein as A, B, contains about cobalt. Catalysts A and B contain no manganoins oxide while C and D contain about 1.22% manganous oxide. In catalysts Cand D the residuum sodium was about 0.25%. Each catalyst was pelleted using a binder of stearic acid and starch as previously described. f 1

In the respective operations identical apparatus was used. An equal volume of the catalyst was to the filtrate 1500 grams of Snow Floss and r placed in a reaction chamber maintained under a pressure .of about 3000 pounds per square inch and at a temperature of about 700 F. Careful- -1y controlled amounts of an olefin mixture and anhydrous ammonia were passed together in contact with the catalyst in the reaction chamber fora period of 12 hours. I Thereafter, the feed of the reactants was discontinued, the chamber purged and the catalyst therein reactivated by passing hydrogen in contact with the catalyst at a temperature of 650-750 F., for a period of 12 I hours, the chamber purgedof hydrogen and the means of a' filtration and stirring: procss. In

this washing operation, the is filtered and the filtercake reslurried in about 10 to 15 gallonsof distilled water. The resultant slurry is then filtered and the washing operation thus continued until the sodium ion concentration in the catalyst has been "reduced to the desired extent, preferably not to exceed about 0.1% of sodium based on the weight of complete cata- After the washing operation has been completed, the flltercake, is slurried thoroughly in about 5" gallons-'ofdistilled water. and to this slurry there'is added about- 5 gallons of water in which there has'been dissolved 103.5 grams of manga'nous acetate 'tetrahydrate, the equivalent of 30 gramsfot M110. Thereafter, the mix- -.ture is'stirred' forabout 6 hours and filtered.- The cake is dried in a steam chest ts: about 4s amination resumed for a period of 12 hours, aiter which, the catalyst was again reactivated and the alternate amination operation and reactivation repeated for the total periods of amination operation hereinafter indicated.

The products of. the reaction and any unreacted materials were passed from the reaction chamber toa stabilizer and the separated materials analyzed. In each operation, the composition of the feed, the feed rates, proportionsof olefin tofammonia and space velocities, i. e. volwere comparable.

In each of these illustrative operations, the charging stock consisted of anhydrous ammonia ume of liquid per volume of catalyst per hour,

and a refinery olefin mixture comprising about 35% by volume of oleflns, predominantly propylene.

The percentage of reduced cobalt, crushing strength, apparent density and extent of reduction of the respective catalyst were as follows, the extent ot'reduction being indlcated'by the relafrom the reaction chamber. Though, in the used I the pellets was experi v enced, the disintegration' of v the case The reduction in disintegration rate of cracking.

1 carbon as catalyst D.

ashramv In the foregoing tabulation the 'valuesgiven for percentage of reduced cobalt were arrived at by dividing the ]percentage of metal found by analysis by the percentage of'metal plus the percentage of the support, each by weight, the per benta'ge of supportbeing taken as-100% metal oxide) metal 7 metal'foun'dX of amination operation and I The total hours I of sulfur andv of carbon dethe weight percent positedon the catalyst duringthe respective total -operating periods were as follows: f a

A B O D 'lotal hours of operation.; 197 144 to 156' We ght per oentsullur on cat 0. 02 0.01 0. 03' 0. 01 Weight per cent carbon on out 12.36 12. 52 3. 2 8.

Thus, it. appears that, in the use ofcatalyst B and D over comparable periods, the amounts of sulfur contamination were equal but the amoum of carbon deposited on D, the cobalt catalyst promoted by manganous oxide, was only about 65% that =deposited onthe catalyst B, the unpromoted I cobalticatalyst.

In the operations in which catalysts A and B I, were used, the catalyst packed so severely in the reaction chamber that it was necessary to usea drill to remove it from the chamber at the end otthe' indicated period of operation. The catalysts C and D were muchmore readily removed each of these catalysts some disintegration of the pellets of catae lystsp and D, which contained the mansanous oxidepromoter, was very much less than that in r of the pellets together with the much slower rate-of carbon deposition are indicative of a reduction in the Evidenceof th correlation of carbon deposition uponthe c talyst and disintegrationof the catalyst appears from a consideration of results obtained using the two promoted catalysts C and D. Catalyst C was in operation about 60% as long as catalyst D but thereafter the catalyst C was found to contain only about 40% as much v This is reflected in the" amount of disintegration.

At the end of the operation catalyst C was removed from the. reaction chamber with a minimum of difliculty-andwas found to contain'only about by weight of fines. Catalyst D was less eas'ily removed and contained about 50% fines. These results indicated that cracking with as long where manganous oxide-promoted catalyst for the unpromoted catalyst. 1

' product from agiven operation.

iluence upon the yield of the desired nitrogen as previously noted, chin graticn or the catalyst increases the resistan oi the catalyst bed to flow pf thereactants and the reactivating hy- 'drogen therethrough. In this illustrative series of operations, disintegration oi the catalyst was closely observed by measuring the resistance of gan to show any appreciable increase. These back tal processing time before plonltrlle and trative operations.

ofthe unpromoted catalysts, IA and B.

fluent gases.

Olefin, wt. percent consumed A B C D Unr acted--. 17.5 22s -11.s 11.1 To gaiaflin 50. 9 46. O 62. 1 65. 0

. To nitrogen product. 2i. 7 17. 9 16. 9 19. 3 ci'dckd'. 10. O 1.1. 3 6. 5- 4. 4 Unaccounted for 0.1 2.0 2.7 0.2

consequent carbon deposition is an important factor in" catalyst life. Consequently, a repression of the competitive cracking reaction not only avoids lossof valuable reactants but prolongsthe I useful life of the catalyst,

thus having'a dual ingen flow through the bed to -a comparison liable indication of the the flow of hydrogen through the catalytic bed following each intermittent reactivatiug period. This was done by increasing the rate of hydrohour and holding thisrate constant while. measuring the pressure drop through the reactor. By

of this back pressure through freshly reduced catalyst, a rephysical character of the catalyst at any particular time was obtained.

' Under these comparable, operating conditions,

catalysts .Ajand'B each showed a decided back pressure increase, indicating material disintegration, after about 40 to 50 hours oitotal amine.- tion operation. C was quite normal after 96 hours oizoperation and catalyst D remained in use a total of hours before the resistance to hydrogen flow bepressure measurements tion of the catalystis is employed as it is v The prolongation of theguseiul life of the catalyst is a highly beneficial attribute of my present invention. However, in addition thereto. the purity of the'product is materially improved. The advantages obtained by the use of my invention with respect to the repression of appear from-the following tabulated results d erived from of the products. The values presented are average values taken-for the first eight amination polymerization The percentages of propionitrile and of polymers produced and the ratio of polymers to total nitrogen fixation are based on the amount of oleiins charged.

A B o p oEN roduced percent 22.1 an 20.4 22.7 Poiym rs reduced... do. 5.2 4 2.5 3 I Polymers -flxatiou do. 23.3 20 11.7 13.2

The advantages .of myinvention, particularly with respect to the repression of cracking, fur-; the? appears from the following tabulation showing the way in which the olefin was consumed. These are likewise average values and As to total nitrogen fixation, the manganous such as C and D have be as active as the un-,

five cubic feet per 1 pressurewith the basis.

The back pressure of catalyst the production of properiods of each of the four illus-- were derived iromanalyses of the product and of the eftrileaswasobtainedhithc been used with excellent mutt. also. miller .andstilllowertemperaturesmaybeemploycd generally been found to be somewhat increased owesthatresultingiromtheueeodtheunpromotedl cobalt catalyst. However-atlas advantages ot-decreased polymerization and cracking ier outweigh'the' disadvantages of increased hydro- Bahamas-the product of thela el' reaction does not remain as acontaminantin the stawhereas, the products or p l!- m do so remain. This increased selectivity resulting in a lower rate of polym r formationisespeciallyimportantwithrespecttothe purity of the productobtalnedby fractionation.

hoomposites mplccfthe-sproductobtainedin accordance with my improved process and oi'the product obtained under comparable conditions,

theunvrcmoted eobttlteatulrstwasv used, were subiected to fractionation inn-oneinch siedmancolumnand it was round that the product producedusingmymanganous atideprometer contained 127% as snuch acetonitrile, 103% as much propionitrile, 88% as much isobutyronitrile and 95% as muchnormal butyroni product produced usins the cat alyst. 'i'he acetonitrile fraction obtained from the manganous oxide-prometed operation especially pure composed with that obwfi fine the lmprmnoted catalyst,

which illustrates that the formation of hydrocarbonsinthisboilingrangeieminhnisedbythe prom catalyst. The ratio of Monitrile to total nitrileapresentwas about 33% ineachcomposite However,,.in the product result- 'ing from the promoted catalyst, about of the totalnitrogenoithestabiliaed producthasbeen' doundtobepresem:

H in iraetions of boiling ranges above thato! butyronitrile. Y

Itwfllbeunderstoodtha'ttheinventio isaenerally applicable to the catalytic amination oi oleiine b treatment with ammonia in the pieswith advantage. The pressure may also be varied over a considerable range.

The invention has been round particularly a plicable to theamination of propslene tor the m'oduction'ot propionitrile and nitriles containlnI 2. Q-ormorecarbonatoms. Oitbe 8 carbon atom nitrogen compounds produced in'theamination or propylene ml' lonltrilepredominates. However, minor proportions. of the-order at about 5%. o'i-isopropyl aminehasbeeniound tobepresent in the product e I claim: I U 1. In the production oi organic compounds containing nitrogenwhe'rein an oleiiniehydrocarban is reacted with ammonia at'an elevated temperature and min the presence of a catalyst comprisingcobalt suspended on aicarrier the improvement which comprises promoting the susby the prescnce'oi man- 7 containing nitrogen wherein oleflnic hydrocarbon is reacted with ammonia at an elevated temperature and! pressure in the presence of a catalyst comprising about 50% cobalt'suspended on a diatomaceous silica catalyst; the improvementwhich comprises promoting the suspended cobalt catalyst by the presence 0! about 1% manganous oxide, the percentages of cobalt and manganous 40 oxide being based on the total weight of catalyst.

4. In the production oi organic compounds containing nitrogen wherein propylene is reacted with ammonia at an elevated temperature and pressur'e'in the presence oi a catalyst comprising about cobalt suspended on adiatomaceous 'enceoi'asuspendedcobaltcatalystundereleillustrative operations; tor example i850 It, have silica catalyst, the improvementr which comprises promoting the suspended cobalt catalyst by' the presence of about 1% manganous oxide, the per centages or cobalt and manganous oxide being based on the total weight'ot catalyst.

JOHN W. 'I'Ill'lllt. 

